Langmuir, Vol.29, No.1, 474-479, 2013
Synthesis and Electrochemistry of 6 nm Ferrocenated Indium-Tin Oxide Nanoparticles
Indium-tin oxide (ITO) nanoparticles, 6.1 +/- 0.8 nm in diameter, were synthesized using a hot injection method. After reaction with 3-aminopropyldimethylethoxysilane to replace the initial oleylamine and oleic acid capping ligands, the aminated nanoparticles were rendered electroactive by functionalization with ferrocenoyl chloride. The nanoparticle color changed from blue-green to light brown, and the nanoparticles became more soluble in polar solvents, notably acetonitrile. The nanoparticle diffusion coefficient (D = 1.0 x 10(-6) cm(2)/s) and effective ferrocene concentration (C = 0.60 mM) in acetonitrile solutions were determined using ratios of DC and (DC)-C-1/2 data measured by microdisk voltammetry and chronoamperometry. The D result compares favorably to an Einstein Stokes estimate (2.1 x 10(-6) cm(2)/s), assuming an 8 nm hydrodynamic diameter in acetonitrile (6 nm for the ITO core plus 2 nm for the ligand shell). The ferrocene concentration result is lower than anticipated (ca. 1.60 mM) based on a potentiometric titration of the ferrocene sites with Cu(II) in acetonitrile. Cyclic voltammetric data indicate tendency of the ferrocenated nanoparticles to adsorb on the Pt working electrode.